Ultrafast Excited State Dynamics and Fluorescence from Vitamin B12 and Organometallic [Co]-C≡C-R Cobalamins
Cobalamins are cobalt-centered cyclic tetrapyrrole ring-based molecules that provide cofactors for exceptional biological processes and possess unique and synthetically tunable photochemistry. Typical cobalamins are characterized by a visible absorption spectrum consisting of peaks labeled α, β, and sh. The physical basis of these peaks as having electronic origin or as a vibronic progression is ambiguous despite much investigation. Here, for the first time, cobalamin fluorescence is identified in several derivatives. The fluorescence lifetime is ca. 100-200 fs with quantum yields on the order of 10-6-10-5 because of rapid population of "dark" excited states. The results are compared with the fluorescent analogue with zinc replacing the cobalt in the corrin ring. Analysis of the breadth of the emission spectrum provides evidence that a vibrational progression in a single excited electronic state makes the dominant contribution to the visible absorption band.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:124 |
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| Enthalten in: |
The journal of physical chemistry. B - 124(2020), 30 vom: 30. Juli, Seite 6651-6656 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Salerno, Elvin V [VerfasserIn] |
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| Links: |
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| Themen: |
3G0H8C9362 |
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| Anmerkungen: |
Date Completed 14.05.2021 Date Revised 14.05.2021 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/acs.jpcb.0c04886 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM312684398 |
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| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Cobalamins are cobalt-centered cyclic tetrapyrrole ring-based molecules that provide cofactors for exceptional biological processes and possess unique and synthetically tunable photochemistry. Typical cobalamins are characterized by a visible absorption spectrum consisting of peaks labeled α, β, and sh. The physical basis of these peaks as having electronic origin or as a vibronic progression is ambiguous despite much investigation. Here, for the first time, cobalamin fluorescence is identified in several derivatives. The fluorescence lifetime is ca. 100-200 fs with quantum yields on the order of 10-6-10-5 because of rapid population of "dark" excited states. The results are compared with the fluorescent analogue with zinc replacing the cobalt in the corrin ring. Analysis of the breadth of the emission spectrum provides evidence that a vibrational progression in a single excited electronic state makes the dominant contribution to the visible absorption band | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 650 | 7 | |a Vitamins |2 NLM | |
| 650 | 7 | |a Cobalt |2 NLM | |
| 650 | 7 | |a 3G0H8C9362 |2 NLM | |
| 650 | 7 | |a Vitamin B 12 |2 NLM | |
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| 700 | 1 | |a Miller, Nicholas A |e verfasserin |4 aut | |
| 700 | 1 | |a Konar, Arkaprabha |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Yan |e verfasserin |4 aut | |
| 700 | 1 | |a Kieninger, Christoph |e verfasserin |4 aut | |
| 700 | 1 | |a Kräutler, Bernhard |e verfasserin |4 aut | |
| 700 | 1 | |a Sension, Roseanne J |e verfasserin |4 aut | |
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